CN110313087A - Sintered lithium complex oxide plate - Google Patents

Sintered lithium complex oxide plate Download PDF

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Publication number
CN110313087A
CN110313087A CN201880005559.XA CN201880005559A CN110313087A CN 110313087 A CN110313087 A CN 110313087A CN 201880005559 A CN201880005559 A CN 201880005559A CN 110313087 A CN110313087 A CN 110313087A
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complex oxide
lithium complex
sintered
oxide plate
lithium
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CN110313087B (en
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由良幸信
小林伸行
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NGK Insulators Ltd
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NGK Insulators Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention discloses a kind of sintered lithium complex oxide plate, it is the sintered lithium complex oxide plate of the anode for lithium secondary battery, sintered lithium complex oxide plate has: multiple primary particles with layered rock salt structure combine obtained structure, and, the porosity is 3~30%, average air aperture is 15 μm or less, open pore ratio is 70% or more, with a thickness of 40~200 μm, the average grain diameter of multiple primary particles, i.e. primary particle size is 20 μm or less, the peak number of gas pore-size distribution is 1, volume reference D10, D50 and D90 stomata diameter meets D50/D10 >=2.5, the relationship of D90/D50 >=2.5 and D90/D10 >=8.0.According to the present invention, thicker sintered lithium complex oxide plate is provided, with high-energy density, also, in the case where being assembled in lithium secondary battery as anode, the excellent properties such as resistance to bend(ing), rapid charge characteristic can be showed.

Description

Sintered lithium complex oxide plate
Technical field
The present invention relates to the sintered lithium complex oxide plates of the anode for lithium secondary battery.
Background technique
As the positive electrode active material layer of lithium secondary battery (also referred to as lithium ion secondary battery), it is known that powder point The anode for dissipating type, is by the powder and adhesive, conductive agent of lithium composite xoide (typically lithium transition-metal oxide) Equal additives are kneaded, are formed.Since the anode of powder dispersing type includes that more (such as 10 weight % are left for content It is right) do not have helpful adhesive to capacity, so, the packed density drop of lithium composite xoide as a positive electrode active material It is low.Therefore, there are biggish improvement leeway in terms of capacity, efficiency for charge-discharge for the distributed anode of powder.
Then, it attempts: wanting by constituting anode or positive electrode active material layer using sintered lithium complex oxide plate To improve capacity, efficiency for charge-discharge.In this case, due to being free of adhesive in anode or positive electrode active material layer, so lithium The packed density of composite oxides increases, thus it can be expected that obtaining high capacity and good efficiency for charge-discharge.
For example, a kind of anode of lithium secondary battery is disclosed in patent document 1 (No. 5587052 bulletins of Japanese Patent Publication No.), Have: positive electrode collector and the positive electrode active material layer engaged by electric conductivity bonding layer with positive electrode collector.The anode Active material layer includes: compound with a thickness of the lithium that 30 μm or more, voidage are 3~30%, open pore ratio is 70% or more Oxidate sintered body plate.In addition, sintered lithium complex oxide plate has: partial size is 5 μm or less and has layered rock salt structure The obtained structure of the multiple combinations of primary particle, also, in X-ray diffraction, the diffracted intensity of (003) crystal face relative to (104) ratio [003]/[104] of the diffracted intensity of crystal face are 2 or less.
A kind of lithium of anode for lithium secondary battery is disclosed in patent document 2 (No. 5752303 bulletins of Japanese Patent Publication No.) Composite oxide sintered body plate, the sintered lithium complex oxide plate with a thickness of 30 μm or more, voidage is 3~30%, is opened Implication hole ratio is 70% or more.In addition, the sintered lithium complex oxide plate has: partial size is 2.2 μm or less and has layer The structure that the multiple combinations of the primary particle of shape rock salt structure obtain, also, in X-ray diffraction, the diffracted intensity of (003) crystal face Ratio [003]/[104] of diffracted intensity relative to (104) crystal face are 2 or less.
A kind of lithium of anode for lithium secondary battery is disclosed in patent document 3 (No. 5703409 bulletins of Japanese Patent Publication No.) Composite oxide sintered body plate, the sintered lithium complex oxide plate have multiple primary particles and combine obtained structure, once The size of particle, i.e. primary particle size are 5 μm or less.In addition, sintered lithium complex oxide plate with a thickness of 30 μm or more, it is average Stomata diameter is 0.1~5 μm, and voidage is 3% more than and less than 15%.Similarly, X is penetrated the sintered lithium complex oxide plate Ratio [003]/[104] of diffracted intensity of in line diffraction, (003) crystal face the diffracted intensity relative to (104) crystal face be 2 with Under.
Patent Documents 1 to 3 all solve the problems, such as follows, that is, the filling rate mistake of the lithium composite xoide in sintered body plate High region, cycle characteristics (capacity maintenance characteristics when charge and discharge cycles are repeated) deteriorate.Specifically, cycle characteristics is disliked The reason of change, is that the crystal boundary in sintered body plate cracks (hereinafter referred to as grain-boundary crack), and sintered body plate with lead (hereinafter referred to as joint interface removing) is removed in the interface of electrical bonding layer, by inhibiting above-mentioned grain-boundary crack and joint interface The generation of removing, is able to solve the above problem.
Existing technical literature
Patent document
Patent document 1: No. 5587052 bulletins of Japanese Patent Publication No.
Patent document 2: No. 5752303 bulletins of Japanese Patent Publication No.
Patent document 3: No. 5703409 bulletins of Japanese Patent Publication No.
Summary of the invention
However, in recent years, the demand to the small-sized electrochemical cell of smart card, wearable device improves.In order to realize Gao Rong Amount and high-energy density are burnt in the anode or positive electrode active material layer of above-mentioned small-sized electrochemical cell using thicker lithium composite xoide Knot body plate is most convenient.It on the other hand, can be according to its use for the small-sized electrochemical cell of smart card, wearable device Mode and require it with distinctive performance.For example, for the battery used in the environment of being easy by bending stress, it is desirable to It, which has, is directed to curved tolerance (hereinafter referred to as resistance to bend(ing)).In addition, in user's portable environment always The lower battery used, it is desirable to which it is with rapid charge characteristic.
It has recently been discovered by the inventor of the present invention that by defined sintered lithium complex oxide plate by gas pore-size distribution Control is distinctive distribution (profile), a kind of thicker sintered lithium complex oxide plate is capable of providing, with high-energy Density, also, in the case where being assembled in lithium secondary battery as anode, resistance to bend(ing), rapid charge characteristic can be showed Equal excellent properties.
Therefore, the object of the present invention is to provide a kind of thicker sintered lithium complex oxide plates, with high-energy Density, also, in the case where being assembled in lithium secondary battery as anode, resistance to bend(ing), rapid charge characteristic can be showed Equal excellent properties.
A scheme according to the present invention provides a kind of sintered lithium complex oxide plate, be for lithium secondary battery just The sintered lithium complex oxide plate of pole, wherein the sintered lithium complex oxide plate has: with layered rock salt structure Multiple primary particles combine obtained structure, also,
The porosity is 3~30%,
Average air aperture be 15 μm hereinafter,
Open pore ratio is 70% or more,
With a thickness of 40~200 μm,
The average grain diameter of the multiple primary particle, i.e. primary particle size be 20 μm hereinafter,
The peak number of gas pore-size distribution is 1,
Volume reference D10, D50 and D90 stomata diameter meet D50/D10 >=2.5, D90/D50 >=2.5 and D90/D10 >=8.0 relationship.
Specific embodiment
Definition
Hereinafter, providing the definition for determining parameter of the invention.
" porosity " is in this specification: in sintered lithium complex oxide plate, stomata (including open pore and close Implication hole) volume ratio.The porosity can carry out image analysis by the cross-sectional SEM image to sintered body plate to measure. For example, sintered body plate is processed using Cross section polishing machine (CP), grinding section is exposed.Utilize SEM (scanning electron Microscope) with defined multiplying power (such as 1000 times) and the defined visual field (such as 125 μm of 125 μ ms) observe the grinding cut Face.Image analysis carried out to obtained SEM image, the areas of whole stomatas in the visual field divided by the sintered body plate in the visual field face Product (sectional area) obtains quotient, thus obtained quotient obtains the porosity (%) multiplied by 100.
" average air aperture " is in this specification: measure for sintered lithium complex oxide plate, horizontal axis is gas Volume in aperture, the gas pore-size distribution (integrating distribution) that the longitudinal axis is (relative to total pore volume 100%) cumulative volume % Benchmark D50 stomata diameter.Well known volume reference D50 partial size in the meaning of volume reference D50 stomata diameter and the size distribution of powder It is identical.Therefore, volume reference D50 stomata diameter refers to: accumulation pore volume is 50% stomata diameter of total pore volume.It can make With mercury porisimetry, gas pore-size distribution is measured using mercury injection method.
In this specification " open pore ratio ": open pore relative to including in sintered lithium complex oxide plate The volume ratio (volume %) of all stomatas (including open pore and closed pore)." open pore " refers to: sintered body plate In include stomata in the external stomata being connected to sintered body plate." closed pore " refers to: the gas for including in sintered body plate The stomata being connected to without the outside with sintered body plate in hole.Open pore ratio can be suitable according to being found out by bulk density Total total porosity in open pore and closed pore and the silent gas for being equivalent to closed pore that is found out by apparent density Porosity is simultaneously found out by calculating.Archimedes method etc. can be used to measure in parameter for calculating open pore ratio.Example Such as, it can be found out closed porosity (volume %) by the apparent density measured using Archimedes method, it on the other hand, can be with Total porosity (volume %) is found out by the bulk density measured using Archimedes method.It is then possible to according to closed pore Rate and total porosity simultaneously find out open pore ratio by calculating below.
(open pore ratio)=(apparent porosity)/(total porosity)
=(apparent porosity)/[(apparent porosity)+(closed porosity)]
=[(total porosity)-(closed porosity)]/(total porosity)
" primary particle size " is in this specification: constituting the average grain of multiple primary particles of sintered lithium complex oxide plate Diameter.The primary particle size can carry out image analysis by the cross-sectional SEM image to sintered body plate to measure.For example, by sintered body Plate is processed using Cross section polishing machine (CP), and grinding section is exposed.Using SEM (scanning electron microscope) to provide Multiplying power (such as 1000 times) and the defined visual field (such as 125 μm of 125 μ ms) observe the grinding section.At this point, with the visual field The interior mode there are 20 or more primary particles sets the visual field.It is drawn for all primary particles in obtained SEM image Circumscribed circle finds out these external diameter of a circles at this time, using their average value as primary particle size.
" peak number of gas pore-size distribution " is in this specification: measuring for sintered lithium complex oxide plate, horizontal The quantity at the peak in gas pore-size distribution (frequency distribution) that axis is stomata diameter, the longitudinal axis is volume %.Peak is defined as stomata diameter point The point that inflection point in cloth and 10 before and after it or more continuously increase or continuously reduce.Mercury porisimetry can be used And gas pore-size distribution is measured using mercury injection method.
" volume reference D10, D50 and D90 stomata diameter " is in this specification: surveying for sintered lithium complex oxide plate Surely obtain, horizontal axis is stomata diameter, the gas pore-size distribution that the longitudinal axis is (relative to total pore volume 100%) cumulative volume % Volume reference D10, D50 and D90 stomata diameter in (integrating distribution).The meaning of volume reference D10, D50 and D90 stomata diameter It is identical as volume reference D10, D50 well known in the size distribution of powder and D90 partial size.Therefore, volume reference D10, D50 with And D90 stomata diameter refers to: accumulation pore volume is respectively 10%, 50% and 90% stomata diameter of total pore volume.It can be with Gas pore-size distribution is measured using mercury porisimetry and using mercury injection method.
Sintered lithium complex oxide plate
Sintered lithium complex oxide plate of the invention is used for the anode of lithium secondary battery.The sintered lithium complex oxide Plate has: multiple primary particles with layered rock salt structure combine obtained structure.In addition, sintered lithium complex oxide plate The porosity be 3~30%, average air aperture is 15 μm hereinafter, open pore ratio is 70% or more, with a thickness of 40~200 μ m.In addition, average grain diameter, the i.e. primary particle size of multiple primary particles of sintered lithium complex oxide plate is 20 μm hereinafter, stomata The peak number of diameter distribution is 1, volume reference D10, D50 and D90 stomata diameter meet D50/D10 >=2.5, D90/D50 >=2.5 with And the relationship of D90/D10 >=8.0.By like this in defined sintered lithium complex oxide plate by stomata diameter distributed controll For distinctive distribution, it is capable of providing thicker sintered lithium complex oxide plate, with high-energy density, also, in conduct In the case that anode is assembled in lithium secondary battery, the excellent properties such as resistance to bend(ing), rapid charge characteristic can be showed.
As described above, in order to realize high capacity and high-energy density, in the anode or positive active material of small-sized electrochemical cell Layer is most convenient using thicker sintered lithium complex oxide plate.However, for smart card, wearable device it is small-sized Electrochemical cell can require it with distinctive performance according to its usage mode.For example, for being easy by bending stress The battery used under environment, it is desirable to which it, which has, is directed to curved tolerance (hereinafter referred to as resistance to bend(ing)).In addition, for using The battery that person uses in the environment of carrying always, it is desirable to which it is with rapid charge characteristic.However, only will be previous to having Sintered lithium complex oxide plate thicken obtained by positive plate and organic electrolyte or ionic liquid, liquid high-energy Densitybattery (slim lithium battery) carries out bend test, as a result distinguishes, the sustainment rate of capacity reduces or short circuit.In addition, with height Multiplying power (2C) carries out charge and discharge cycles test to same liquid high energy density cells (slim lithium battery), as a result also distinguishes, The sustainment rate of capacity reduces.In this regard, sintered lithium complex oxide plate of the invention according to the above configuration, even if The cyclic test under bend test or high magnification is carried out, the deterioration of battery performance can be also prevented or inhibited.Although its reason is not It determines, however, it is believed that the reason is that: the stress generated when the stress generated when bending and charge and discharge is (as caused by dilation Non-uniform stress) disperse or mitigate well because of above-mentioned distinctive gas pore-size distribution etc..As a result think, lithium of the invention is multiple It closes oxidate sintered body plate thickness and there is high-energy density, in the case where being assembled in lithium secondary battery as anode, Neng Goucheng Reveal the excellent properties such as resistance to bend(ing), rapid charge characteristic.
Sintered lithium complex oxide plate has: multiple (i.e. a variety of) primary particles with layered rock salt structure combine The structure arrived.Therefore, these primary particles are made of the lithium composite xoide with layered rock salt structure.Lithium composite xoide Typical scenario is: by LixMO2(0.05 < x < 1.10, M are at least one kind of transition metal, and it includes from such as Co, Ni and Mn 1 kind or more of middle selection) indicate oxide.Typical lithium composite xoide has layered rock salt structure.Layered rock salt structure Refer to: the transition metal layer other than lithium layer and lithium is across the alternately stacked crystalline texture of oxygen layer.That is, it can be said that stratiform rock salt knot Structure is: transition metal ions layer and lithium individual course alternately stacked crystalline texture (the typically α-by oxide ion NaFeO2Type structure: transition metal and the lithium structure regularly arranged along [111] axis direction of cubic crystal rock-salt type structure).
It as the preference of the lithium composite xoide with layered rock salt structure, can enumerate: cobalt acid lithium LipCoO2(formula In, 1≤p≤1.1), lithium nickelate LiNiO2, LiMn2O4 Li2MnO3, nickel ion doped Lip(Ni0.5, Mn0.5)O2, by general formula: Lip (Cox, Niy, Mnz)O2(in formula, 0.97≤p≤1.07, x+y+z=1) indicate solid solution, by Lip(Cox, Niy, Alz)O2(formula In, 0.97≤p≤1.07, x+y+z=1,0 x≤0.25 <, 0.6≤y≤0.9 and 0 z≤0.1 <) indicate solid solution, with And Li2MnO3With LiMO2The solid solution of (transition metal such as M Co, Ni), particularly preferably cobalt acid lithium LipCoO2(in formula, 1≤p ≤ 1.1), such as LiCoO2.It should be noted that sintered lithium complex oxide plate can further include Mg, Al, Si, Ca, Ti, V, one or more of elements such as Cr, Fe, Cu, Zn, Ga, Ge, Sr, Y, Zr, Nb, Mo, Ag, Sn, Sb, Te, Ba, Bi.
Constitute sintered lithium complex oxide plate multiple primary particles average grain diameter, i.e. primary particle size for 20 μm with Under, preferably 15 μm or less.For primary particle size, typically 0.1 μm or more, more typically 0.5 μm or more.In general, one Secondary partial size is smaller, and the quantity of crystal boundary is more.Also, the quantity of crystal boundary is more, and the adjoint lattice of charge and discharge cycles produces when flexible Raw internal stress can more disperse well.In addition, in the case where even producing crackle and the quantity of crystal boundary is got over It is more, more crackle can be inhibited to stretch well.On the other hand, in preferred embodiment of the invention, the particle of sintered body intralamellar part Orientation is consistent, as a result, is not easy to apply stress to crystal boundary, even if cycle performance is also excellent under big partial size.In addition, in grain In the biggish situation of diameter, grain boundaries stop charge and discharge when lithium ion diffusion the case where tail off, be conducive to high speed charge and discharge.
Sintered lithium complex oxide plate includes stomata.It include stomata by sintered body plate, so that because in charge and discharge cycles Lithium ion enter and leave the flexible of adjoint lattice and the stress that generates using the stomata and good (uniform) discharge.Therefore, Inhibit to generate grain-boundary crack with repeated charge-discharge cycles as much as possible.In addition, by with the interface of electric conductivity bonding layer institute The stomata (open pore) for including, so that bond strength improves.Therefore, above-mentioned joint interface can be inhibited to remove well The reason of occurring, the removing occurs is: causing lithium multiple because the lithium ion in charge and discharge cycles enters and leaves due to adjoint lattice stretches The shape for closing oxidate sintered body plate changes.Therefore, good cycle characteristics is able to maintain that, further, it is possible to realize Gao Rong Quantization.
The open pore ratio of sintered lithium complex oxide plate is 70% or more, more preferably 80% or more, further Preferably 90% or more.Open pore ratio can be 100%, and typically 98% hereinafter, more typically 95% or less.It is logical Crossing makes 70% or more open pore ratio, so that stress is easier to discharge, effectively inhibits the generation of grain-boundary crack.Think it Reason is as follows.As described above, the dilation of the volume in anode is because the lithium ion in lattice enters and leaves.Open pore be by The stomata that the bread that lithium ion enters and leaves encloses.It is therefore contemplated that: for open pore compared with closed pore, the effect for discharging stress is high.Separately Outside, by making 70% or more open pore ratio, above-mentioned joint interface removing can be effectively inhibited.It is thought that because are as follows: Open pore can be as surface roughness, and by the importing of open pore, bond strength reason surface roughness increases institute's band Come Anchoring Effect and improve.In addition, there are electrolyte, conductive materials etc. by making in open pore, so that the open pore Inner wall play a role well as the face that lithium ion enters and leaves.Therefore, if making 70% or more open pore ratio, Then with the situation larger with the ratio of closed pore existing for the form of simple stomata (not having helpful part to charge and discharge) It compares, multiplying power property is improved.
The porosity of sintered lithium complex oxide plate be 3~30%, more preferably 5~30%, further preferably 7~ 30%, particularly preferably 10~25%.In the case where the porosity is less than 3%, stomata bring stress release effect is insufficient. In addition, the effect of high capacity is significantly attenuated, so undesirable if the porosity is more than 30%.
The average air aperture of sintered lithium complex oxide plate is for 15 μm hereinafter, preferably 12 μm hereinafter, more preferably 10 μ M or less.If average air aperture is more than 15 μm, biggish stomata can be generated.The biggish stomata is not usually complete ball Shape, but the shape being crushed.Therefore, it is easy to concentrate in the locally generation stress of the biggish stomata.Be difficult to obtain as a result, by The effect that stress equably discharges in sintered body.The lower limit value in average air aperture is not particularly limited, from by stomata bring From the viewpoint of stress release effect, average air aperture is preferably 0.03 μm or more, and more preferably 0.1 μm or more.Therefore, if In above-mentioned range, then it can inhibit the generation and joint interface removing of grain-boundary crack well.
The peak number of gas pore-size distribution in sintered lithium complex oxide plate is 1.In addition, sintered lithium complex oxide Volume reference D10, D50 and D90 stomata diameter in plate meet D50/D10 >=2.5, D90/D50 >=2.5 and D90/D10 >= 8.0 relationship.The above-mentioned relation that peak number is 1 means that: stomata diameter is distributed as stable (wider) normal distribution or similar In the distribution of the normal distribution.That is, the relationship of D50/D10 >=2.5 means that: D10 stomata diameter and D50 stomata diameter significantly divide From.The relationship of D90/D50 >=2.5 means that: D50 stomata diameter and D90 are also significantly separated.The relationship of D90/D10 >=8.0 is meaned : D10 stomata diameter and D90 stomata diameter further significantly separate.Therefore, it can be said that above-mentioned 3 relationships are generally speaking meaned : D10 stomata diameter, D50 stomata diameter and D90 stomata diameter mutually significantly separate, that is, stomata diameter wider distribution.Also, recognize Are as follows: disperse stress when stress or the charge and discharge when bending well, can be realized resistance to The excellent properties such as bendability, rapid charge characteristic.
D50/D10 is 2.5 or more, preferably 2.8~20, more preferably 3.0~18.5, further preferably 3.5~17. D90/D50 is 2.5 or more, preferably 2.7~20, more preferably 2.8~18.5, further preferably 3.0~17.1.D90/ D10 is 8.0 or more, preferably 10~150, more preferably 20~135, further preferably 30~120.
In the X-ray diffraction of sintered lithium complex oxide plate, (003) crystal face diffracted intensity (peak intensity) relative to (104) ratio [003]/[104] of the diffracted intensity (peak intensity) of crystal face be preferably 5.0 hereinafter, more preferably 4.0 hereinafter, into One step is preferably 3.0 hereinafter, particularly preferably 2.0 or less.It should be noted that (i.e. to the plate face of sintered lithium complex oxide plate The surface orthogonal with plate thickness direction) carry out above-mentioned X-ray diffraction.Also, if like this peak intensity ratio [003]/[104] compared with Low, then cycle characteristics improves.Think that its reason is as follows.The adjoint lattice of charge and discharge cycles stretch (volume expansion contraction) with (003) maximum on the vertical direction of crystal face (i.e. [003] direction).Therefore, it is easy to be generated in parallel with (003) crystal face by charge and discharge Recycle the flexible caused crackle of adjoint lattice.It in addition, (003) crystal face is the most close fill surface of oxygen, and is lithium ion and electricity Son can not enter and leave, inert face chemically and in electrochemistry.In this regard, as described above, peak intensity ratio [003]/ [104] lower as described above, it is intended that in the plate face of sintered lithium complex oxide plate or engagement circle with positive electrode collector Face, or even reduced in the ratio that the inside of sintered lithium complex oxide plate and plate face occur parallel to (003) crystal face.Also, It is reduced by (003) crystal face in the ratio that joint interface occurs, so that the adhesive strength of joint interface improves, to can inhibit stripping From, also, the generation that grain-boundary crack impact, parallel with plate face is especially reduced to capacity can be effectively inhibited.Cause This, cycle characteristics improves.Peak intensity ratio [003]/[104] lower limit value is not particularly limited, still, typically 1.16 with On, more typically 1.2 or more.
Sintered lithium complex oxide plate with a thickness of 40~200 μm, preferably 50~200 μm, more preferably 80~200 μm, further preferably 100~200 μm.As described above, sintered lithium complex oxide plate is thicker, high capacity more easy to accomplish And the battery of high-energy density.The thickness of sintered lithium complex oxide plate can obtain in the following way, that is, for example sharp The section of sintered lithium complex oxide plate is observed with SEM (scanning electron microscope), and measures sight substantially in parallel at this time Thus distance between the plate face examined obtains above-mentioned thickness.
Manufacturing method
Sintered lithium complex oxide plate of the invention can use any method to manufacture, but, preferably through following (a)~(c) manufacture, that is, the production of the raw cook of (a) containing lithium composite xoide, (b) contain the system of the raw cook of superfluous lithium source Work and (c) stacking and firing of these raw cooks.
(a) production of the raw cook containing lithium composite xoide
Firstly, preparing the raw material powder being made of lithium composite xoide.The powder preferably group becomes LiMO2(M institute as above State) particle (such as the LiCoO synthesized2Particle).The volume reference D50 partial size of raw material powder is preferably 0.1~20 μm.Such as The partial size of fruit raw material powder is larger, then there is stomata bigger tendency.Then, by raw material powder and decentralized medium and various add Add agent (adhesive, plasticizer, dispersing agent etc.) to mix, forms slurry.It, can be for in aftermentioned firing process in slurry The purpose of the compensation of volatile ingredient is added in addition to LiMO in the promotion of grain growth with the degree surplus of 0.5~30mol%2With Outer lithium compound (such as lithium carbonate).Preferably without adding pore forming material in the slurry.It is preferred that slurry is stirred under reduced pressure Deaeration and viscosity is adjusted to 4000~10000cP.It is sheet by obtained sizing material forming, obtains containing lithium combined oxidation The raw cook of object.The raw cook obtained in this way is the formed body of independent sheet.Independent sheet material (otherwise referred to as " self-support film ") is Refer to: can from other supporters it is independent operated with monomer sheet material (also include asperratio be 5 or more it is thin Piece).That is, do not include in independent sheet material fixed engagement in other supporters (substrate etc.) and with the integrated (nothing of the supporter Method separation separates difficulty) sheet material.Sheet forming can use well-known various methods and carry out, but, preferably by Scraper method carries out.The thickness of raw cook containing lithium composite xoide is by the side for becoming desired thickness as described above after firing Formula is suitably set.
(b) production of the raw cook containing superfluous lithium source
On the other hand, it is different from the above-mentioned raw cook containing lithium composite xoide, separately raw cook of the production containing superfluous lithium source. The surplus lithium source be preferably ingredient other than Li by firing disappear in addition to LiMO2Lithium compound in addition.As this The preference of the lithium compound (superfluous lithium source) of sample, can enumerate lithium carbonate.Superfluous lithium source is preferably powdered, superfluous lithium source powder The volume reference D50 partial size at end is preferably 0.1~20 μm, and more preferably 0.2~15 μm.Then, lithium source powder and dispersion are situated between Matter and various additives (adhesive, plasticizer, dispersing agent etc.) mixing, form slurry.It is preferred that obtained slurry is being depressurized Lower stirring deaeration and viscosity is adjusted to 4000~10000cP.It is sheet by obtained sizing material forming, obtains containing surplus The raw cook of lithium source.The raw cook obtained in this way is also the formed body of other independent sheet.Sheet forming can use well-known Various methods carry out, but, carried out preferably by scraper method.The thickness of raw cook containing superfluous lithium source is preferably set to as follows Thickness, that is, the Li content in the raw cook containing superfluous lithium source is relative to the Co content in the raw cook containing lithium composite xoide Molar ratio (Li/Co ratio) is preferably the thickness of 0.1 or more, more preferably 0.1~1.1.
(c) stacking and firing of raw cook
By raw cook (such as the LiCoO containing lithium composite xoide2Raw cook) and containing superfluous lithium source raw cook (such as Li2CO3Raw cook) successively placing is in lower part load bearing board, and uploads in the raw cook containing superfluous lithium source and put portion's load bearing board.It holds on top It burns plate and lower part load bearing board is made of ceramic, be preferably made of zirconium oxide or magnesia.If load bearing board is made of magnesia, There are the tendencies that stomata becomes smaller.Top load bearing board can be porous structure or honeycomb, or compact substance structure.Such as Fruit top load bearing board is compact substance, the then tendency that there are stomatas to become smaller, stomatal number increases in sintered body plate.Then, by these The state that raw cook is clamped with load bearing board, after carrying out degreasing as needed, in the firing temperature (such as 700~1000 DEG C) of middle temperature range It is heat-treated (firing), thus obtains sintered lithium complex oxide plate.The sintered body plate obtained in this way is also other independence Sheet.
(d) brief summary
Above-mentioned preferable production process for the well known manufacturing method recorded in Patent Documents 1 to 3, have with Under feature or difference, and think that these features or difference facilitate all of sintered lithium complex oxide plate of the invention The realization of characteristic.
1) it uses a step process: being disclosed in Patent Documents 1 to 3: being burnt with 1 firing production containing lithium without intermediate sintered body One step process of adult and carry out the production without sintered body among lithium and lithium importing processing (heat treatment, second later Firing) two-step process, but, in above-mentioned preferable production process, using a step process.
2) it uses lithium composite xoide raw material powder: in above-mentioned preferable production process, becoming LiMO using group2(M is as above It is described) particle (such as the LiCoO synthesized2Particle), rather than the particle of the compound of Li, Co etc. is properly mixed.
3) superfluous to use Li (excess quantity: 30mol% or more): (external superfluous by using the raw cook containing superfluous lithium source Lithium source) or superfluous lithium source (internal surplus lithium source) in raw cook containing lithium composite xoide and make in firing that there are mistakes The Li of surplus amount, even if can also control the porosity well in the firing of middle temperature range.External surplus lithium source, which has, reduces stomata Tendency, and internal superfluous lithium source has the tendency for increasing the porosity and average air aperture.
4) firing temperature of temperature range in: by being burnt into middle temperature range (such as 700~1000 DEG C), so that fine gas Hole is easy to leave.
5) size distribution of raw material: compared with the case where using pore creating material, not using the above-mentioned preferably fabricated of pore creating material In method, gap forms gap between particles, and therefore, gas pore-size distribution broadens.
6) load bearing board configuration when being burnt into: by being clampingly burnt into up and down to raw cook laminated body with load bearing board, so that Fine stomata is easy to leave.
As needed and by sintered body plate of the invention be used as positive plate to make laminated cell when, in order to improve and collect The contact or inhibition positive plate of electric body are mobile in inside battery, and sintered body plate can be pasted on to lamination collector.
In addition, slave gamma-butyrolacton, propylene carbonate and the carbonic acid of 96 volume % or more can be contained in the electrolytic solution What is selected in ethyl is one kind or two or more.By using such a electrolyte, in high temperature movement and high temperature work through battery Skill and when making battery, battery manufacture can be steadily carried out, without deteriorating battery.In particular, in the electrolytic solution Not using in the case where ethylene carbonate, alternatively, the containing ratio of ethylene carbonate in the electrolytic solution be 20 volume % with In the case where lower, as negative electrode material, it is preferable to use Li4Ti5O12(LTO)、Nb2TiO7、TiO2Equal ceramic wafers.
In particular, the laminated cell for using sintered lithium complex oxide plate of the invention to make as positive plate can be with With following feature, that is, it is different from common coated electrode, without the adhesive for taking PVDF (Kynoar) as representative. Therefore, it is possible to use: if comprising using PVDF if the adhesive of representative because of high temperature (such as 80 DEG C or more) under adhesive can divide It solves and is not available, the electrolyte comprising the high gamma-butyrolacton of heat resistance.As a result it has the following advantages that, that is, electricity can be made Pond acts at a higher temperature, in addition, battery can be made with 120 DEG C or so of high-temperature technology.
In addition, in the laminated cell for using sintered lithium complex oxide plate of the invention to make as positive plate, it can To use the cathode for being commonly used in lithium secondary battery.As the example of such a common negative electrode material, can enumerate: carbon system The metals such as material, Li, In, Al, Sn, Sb, Bi, Si or semimetal or comprising any one in these metals or semimetal The alloy of kind.In addition it is possible to use lithium titanate (Li4Ti5O12) etc. oxides system cathode.Oxide system cathode can be by metatitanic acid The negative electrode active materials such as lithium mixed with adhesive and conductive auxiliary agent and be coated and the material that makes, or make lithium titanate The ceramic wafer that equal negative electrode active materials are sintered.In the latter case, ceramic wafer can be fine and close ceramic wafer, can also be with For in the internal ceramic wafer comprising open pore.In the case where lithium titanate is used as negative electrode layer, with the feelings for using carbon-based material Condition is compared, and has the advantages that reliability and output performance greatly improve.In addition, compound using lithium titanate anode and lithium of the invention Oxidesintering plate and the lithium secondary battery made show that cycle performance is good and retention good (self discharge is less) etc. Therefore high reliability can make its series connectionization and simply controlling.
As negative electrode active material, TiO can be used2、Nb2TiO7.In this case, negative electrode material can be for will be above-mentioned The mixture of negative electrode active material, adhesive and conductive auxiliary agent is coated and the material that makes, or makes above-mentioned negative The ceramic wafer that pole active material is sintered.In the latter case, ceramic wafer can be fine and close ceramic wafer, or Inside includes the ceramic wafer of open pore.In the case where these materials are used as negative electrode layer, the case where with carbon-based material is used It compares, has the advantages that reliability and output performance greatly improve.In addition, also having compared with the case where using lithium titanate material There is the advantages of energy density raising.In the case where these materials are used as negative electrode layer, in the same manner as the case where using lithium titanate, Also have the advantages that cycle performance, retention etc. are excellent in reliability, can also be easy to carry out series connectionization.
Embodiment
By example below, the present invention is further concretely demonstrated.
Example 1
(1) production of positive plate
(1a)LiCoO2The production of raw cook
Firstly, by LiCoO2Raw material powder (just with chemical Industrial Co., Ltd system) (hereinafter referred to as raw material A) 100 weight Part, decentralized medium (toluene: isopropanol=1:1) 100 parts by weight, adhesive (polyvinyl butyral: model BM-2, ponding Learn Industrial Co., Ltd's system) 10 parts by weight, plasticizer (DOP: phthalic acid two (2- ethylhexyl) ester, dark fund chemical conversion strain formula Commercial firm's system) 4 parts by weight and dispersing agent (ProductName: Rheodol SP-O30, Kao Corp's system) 2 parts by weight mixing. The volume reference D50 partial size of raw material A is 8 μm.Obtained mixture is stirred into deaeration under reduced pressure, also, viscosity is adjusted to 4000cP prepares LiCoO as a result,2Slurry.Viscosity is measured using Brookfield corporation LVT type viscosimeter.By this The slurry of sample preparation is taken shape on PET film by scraper method with sheet, and LiCoO is consequently formed2Raw cook.LiCoO after drying2It is raw Piece with a thickness of 100 μm.
(1b)Li2CO3The production of raw cook (superfluous lithium source)
By Li2CO3Raw material powder (2.5 μm of volume reference D50 partial size, this village Chemical Co., Ltd. system) 100 parts by weight are glued Mixture (polyvinyl butyral: model BM-2, Sekisui Chemical Co., Ltd's system) 5 parts by weight, plasticizer (DOP: adjacent benzene Dioctyl phthalate two (2- ethylhexyl) ester, dark fund are melted into Co. Ltd. system) 2 parts by weight and dispersing agent (Rheodol SP- O30, Kao Corp's system) mixing of 2 parts by weight.Obtained mixture is stirred into deaeration under reduced pressure, also, viscosity is adjusted For 4000cP, Li is prepared as a result,2CO3Slurry.Viscosity is measured using Brookfield corporation LVT type viscosimeter.It will The Li being prepared2CO3Slurry is taken shape on PET film by scraper method with sheet, forms Li as a result,2CO3Raw cook.After drying Li2CO3The thickness of raw cook is set are as follows: Li2CO3Li content in raw cook is relative to LiCoO2The molar ratio of Co content in raw cook, That is Li/Co ratio is 0.5.
(1c)LiCoO2The production of sintered plate
The LiCoO that will be peeled from PET film2Raw cook is cut into 50mm square with cutter, and placing is in the oxygen as lower part load bearing board Change the center of magnesium load bearing board (size 90mm square, height 1mm).By the Li as superfluous lithium source2CO3Raw cook placing in LiCoO2On raw cook, by as the Porous magnesia load bearing board placing of top load bearing board in the surplus lithium source.With by this The state placing that a little raw cook load bearing boards clamp is in the aluminium oxide saggar (Co., Ltd.'s Nikkato system) of 120mm square.This When, it is that aluminium oxide saggar is not closed, but the gap for being spaced apart 0.5mm closes the lid.And it is burnt into as follows, that is, will obtain Sandwich 600 DEG C of progress degreasing in 3 hours is warming up to 200 DEG C/h of heating rate after, be warming up to 900 DEG C with 200 DEG C/h and protect It holds 20 hours.After firing, it is made to be cooled to room temperature, then, sintered body is taken out from aluminium oxide saggar.It obtains like this LiCoO2Sintered plate is as positive plate.Obtained positive plate is laser machined into the shape for 9mm × 9mm squares.
(2) production of battery
By positive plate, partition and cathode successively placing comprising carbon, laminated body is made.The laminated body is impregnated in electricity Liquid is solved, laminated-type battery is thus made.As electrolyte, using making LiPF6It is dissolved in by the concentration of 1mol/L by carbonic acid Asia second Ester (EC) and diethyl carbonate (DEC) are with isometric than solution obtained in the organic solvent that is mixed to get.As partition, make With 25 μm of thickness of polypropylene Porous monofilms (Celgard corporation, Celgard (registered trademark) 2500).
(3) it evaluates
To the LiCoO synthesized in above-mentioned (1c)2The battery made in sintered plate (positive plate) and above-mentioned (2), as follows into The various evaluations of row.
< porosity >
By LiCoO2Sintered plate is carried out using Cross section polishing machine (CP) (Jeol Ltd.'s system, IB-15000CP) Grinding, and by obtained positive plate section with 1000 times of the visual field (125 125 μm of μ m) carry out SEM observation (Japan Electronics system, JSM6390LA).Image analysis is carried out to obtained SEM image, the leachy area of institute obtains quotient divided by positive area, Obtained quotient calculates the porosity (%) multiplied by 100.
< average air aperture >
LiCoO is measured using mercury injection method using mercury porisimetry (Shimadzu Seisakusho Ltd.'s system, Autopore IV9510)2It burns The gas pore-size distribution of the volume reference of knot tying.It is stomata diameter, the stomata that the longitudinal axis is cumulative volume % according to obtain in this way, horizontal axis Diameter distribution curve finds out volume reference D50 stomata diameter, as average air aperture.
< open pore ratio >
LiCoO is found out using Archimedes method2The open pore ratio of sintered plate.Specifically, according to A Ji meter is utilized The apparent density that moral method measures finds out closed porosity, on the other hand, according to the body measured using Archimedes method Product density finds out total porosity.Then, according to closed porosity and total porosity, open pore ratio is found out by calculating below Rate.
(open pore ratio)=(apparent porosity)/(total porosity)
=(apparent porosity)/[(apparent porosity)+(closed porosity)]
=[(total porosity)-(closed porosity)]/(total porosity)
< primary particle size >
By LiCoO2Sintered plate is carried out using Cross section polishing machine (CP) (Jeol Ltd.'s system, IB-15000CP) Grinding, and by obtained positive plate section with 1000 times of the visual field (125 125 μm of μ m) carry out SEM observation (Japan Electronics system, JSM6390LA).At this point, by the visual field there are 20 or more primary particles in the way of set the visual field.To obtained SEM image In all primary particles draw circumscribed circle, these external diameter of a circles at this time are found out, using their average value as primary Partial size.
< plate thickness >
By LiCoO2Sintered plate is carried out using Cross section polishing machine (CP) (Jeol Ltd.'s system, IB-15000CP) Grinding carries out SEM observation (Japan Electronics system, JSM6390LA) to obtained positive plate section, measures the thickness of positive plate.It answers Explanation is given, the LiCoO about process (1a), after aforementioned drying is measured in the same manner as aforesaid operations2The thickness of raw cook.
< degree of orientation >
Using XRD device (Co., Ltd. Neo-Confucianism's system, RINT-TTR III), to LiCoO2The surface (plate face) of sintered plate X-ray irradiation measures XRD distribution map at this time.By in X-ray diffraction, (003) crystal face diffracted intensity relative to (104) Ratio [003]/[104] of the diffracted intensity of crystal face are used as the degree of orientation.
< gas pore-size distribution >
Using mercury porisimetry (Shimadzu Seisakusho Ltd.'s system, Autopore IV9510), LiCoO is measured using mercury injection method2Sintering The gas pore-size distribution of the volume reference of plate.It is stomata diameter, the stomata diameter that the longitudinal axis is cumulative volume % according to obtain in this way, horizontal axis Distribution curve finds out volume reference D10, D50 and D90 stomata diameter, and calculates D50/D10, D90/D50 and D90/D10 Each ratio.In addition, counting the quantity at the peak in the gas pore-size distribution that horizontal axis is stomata diameter, the longitudinal axis is volume %.At this point, by stomata Inflection point in diameter distribution and 10 or more the points for continuously increasing or continuously reducing before and after it are counted as peak Number.
Capacity maintenance rate > after < bend test
Firstly, the initial discharge capacity of measurement battery.The measurement is by being repeated total 3 times following charge and discharge cycles It carries out, and using the average value of obtained discharge capacity as initial discharge capacity, which includes: with 0.2C multiplying power Constant-current charge to cell voltage be 4.2V, next, constant-voltage charge to current value be 0.02C multiplying power after, with 0.2C multiplying power discharging To 3.0V.Next, being bent battery based on JIS X 6305-1:2010, battery after bending is measured as described above Discharge capacity.Calculate the discharge capacity of battery after bending relative to the initial discharge capacity of the battery before bending ratio simultaneously Multiplied by 100, it is thus bent capacity maintenance rate (%) after test.
< high speed charge/discharge capacity sustainment rate >
In the potential range of 4.2V-3.0V, the high speed charge/discharge capacity sustainment rate of battery is measured in the following order.
(i) measurement of discharge capacity is carried out by the way that total 3 times following charge and discharge cycles are repeated, by the flat of them For mean value as initial discharge capacity, which includes: to be connect down with 0.2C multiplying power constant-current charge to cell voltage for 4.2V Come, constant-voltage charge to current value be 0.02C multiplying power after, with 0.2C multiplying power discharging to 3.0V.
(ii) total 50 high speed charge and discharge are carried out with rate of charge 2C and discharge-rate 2C.
(iii) carry out the measurement of discharge capacity by the way that total 3 times following charge and discharge cycles are repeated, by they For average value as discharge capacity after high speed charge and discharge, which includes: with 0.2C multiplying power constant-current charge to cell voltage For 4.2V, next, after with 0.02C multiplying power constant-voltage charge, with 0.2C multiplying power discharging to 3.0V.
(iv) discharge capacity is relative to obtained in above-mentioned (i) after calculating high speed charge and discharge obtained in above-mentioned (iii) The ratio of initial discharge capacity obtains high speed charge/discharge capacity sustainment rate (%) multiplied by 100.
Example 2
1) Li after setting drying in such a way that Li/Co ratio is 0.42CO3The thickness of raw cook, 2) it is used as top load bearing board, make With the zirconium oxide load bearing board of honeycomb, 3) it is used as lower part load bearing board, using zirconium oxide load bearing board, in addition to this, with example 1 Positive plate and battery are similarly made, various evaluations are carried out.
Example 3
In LiCoO2Li is further added in slurry2CO3Raw material powder (2.5 μm of volume reference D50 partial size, this village chemistry strain Formula commercial firm system), make LiCoO2Superfluous Li/Co ratio in raw cook is 0.1, in addition to this, positive plate and electricity is made in the same manner as example 2 Pond carries out various evaluations.It should be noted that above-mentioned surplus Li/Co ratio is: LiCoO2Li is derived from raw cook2CO3Superfluous Li Content is relative to LiCoO2The molar ratio of Co content in raw cook.
Example 4
1) LiCoO of 0.2 μm of volume reference D50 partial size is used2Raw material powder (hereinafter referred to as raw material B) replace raw material A, 2) Li after setting drying in such a way that Li/Co ratio is 0.42CO3The thickness of raw cook, 3) it is used as top load bearing board, use Porous knot The zirconium oxide load bearing board of structure, 4) it in addition to this, is made in the same manner as example 1 as lower part load bearing board using zirconium oxide load bearing board Make positive plate and battery, carries out various evaluations.
Example 5
1) using the LiCoO of 15 μm of the volume reference D50 partial size being fired into through 700 DEG C of firing temperature2Raw material powder (hereinafter referred to as raw material C) replaces raw material A, 2) set in such a way that Li/Co ratio is 0.3 it is dry after Li2CO3The thickness of raw cook, 3) In LiCoO2Li is further added in slurry2CO3Raw material powder (2.5 μm of volume reference D50 partial size, this village Chemical Co., Ltd. System) so that LiCoO2Superfluous Li/Co ratio in raw cook is 0.3,4) it is used as top load bearing board, use compact texture (consistency 90% or more) magnesia load bearing board, 5) it is used as lower part load bearing board, using zirconium oxide load bearing board, in addition to this, with example 1 Positive plate and battery are similarly made, various evaluations are carried out.
Example 6
1) LiCoO of 5 μm of volume reference D50 partial size is used2Raw material powder (hereinafter referred to as raw material D) replace raw material A, 2) LiCoO2Li is further added in slurry2CO3Raw material powder (2.5 μm of volume reference D50 partial size, this village Chemical Co., Ltd. system), So that LiCoO2Superfluous Li/Co ratio in raw cook is 0.1,3) for making LiCoO2The firing temperature of sintered plate is 950 DEG C, and It is not 900 DEG C, in addition to this, positive plate and battery is made in the same manner as example 1, carries out various evaluations.
Example 7
By the LiCoO after drying2Raw cook is formed with a thickness of 200 μm of mode, in addition to this, in the same manner as example 2 Positive plate and battery are made, various evaluations are carried out.
Example 8
By the LiCoO after drying2Being formed with a thickness of 80 μm of mode for raw cook, in addition to this, makes in the same manner as example 2 Make positive plate and battery, carries out various evaluations.
Example 9
By the LiCoO after drying2Being formed with a thickness of 50 μm of mode for raw cook, in addition to this, makes in the same manner as example 2 Make positive plate and battery, carries out various evaluations.
Example 10
1) using raw material powder (the hereinafter referred to as raw material got similarly other than firing temperature is 900 DEG C with raw material C E) replace raw material A, 2) set in such a way that Li/Co ratio is 0.4 it is dry after Li2CO3The thickness of raw cook, in addition to this, with example 1 Positive plate and battery are similarly made, various evaluations are carried out.
Example 11
1) using raw material B replace raw material A, 2) in LiCoO2Li is further added in slurry2CO3Raw material powder (volume reference 2.5 μm of D50 partial size, this village Chemical Co., Ltd. system) so that LiCoO2Superfluous Li/Co ratio in raw cook is 0.1, in addition to this, Positive plate and battery are made in the same manner as example 2, carry out various evaluations.
Example 12
Using the raw material powder (hereinafter referred to as raw material F) for crushing raw material C with ball mill replace raw material A, except this with Outside, positive plate and battery are made in the same manner as example 2, carry out various evaluations.
Example 13
Using making to utilize the spherical Co (OH) of Co deposited synthesis2Obtained synthesis material is reacted in 800 DEG C with LiOH Powder (hereinafter referred to as raw material G) replaces raw material A, in addition to this, positive plate and battery is made in the same manner as example 2, carries out various comment Valence.
Example 14
Raw material is replaced using the mixed raw material powder (hereinafter referred to as raw material H) for being equably mixed to get raw material A, D and E A makes positive plate and battery in the same manner as example 2, carries out various evaluations in addition to this.
Example 15
1) Li after setting drying in such a way that Li/Co ratio is 0.52CO3The thickness of raw cook, 2) for making LiCoO2It burns The firing temperature of knot tying is 800 DEG C, rather than 900 DEG C, in addition to this, positive plate and battery are made in the same manner as example 2, carry out each Kind evaluation.
Example 16(comparison)
1) in LiCoO2Threadiness pore forming material 7.5wt% (Celish PC10S, Daicel are further added in slurry Fine Chem Co. Ltd. system), 2) in LiCoO2Li is further added in slurry2CO3Raw material powder (volume reference D50 partial size 2.5 μm, this village Chemical Co., Ltd. system) so that LiCoO2Superfluous Li/Co ratio in raw cook is 0.3,3) there is no placing Li2CO3 Raw cook and top load bearing board (Porous magnesia load bearing board), 4) for making LiCoO2The firing temperature of sintered plate is 1200 DEG C, rather than 900 DEG C, in addition to this, positive plate and battery are made in the same manner as example 2, carries out various evaluations.
Example 17(comparison)
1) use is comprising relative to Co3O4For be 5wt% Bi2O3Co as auxiliary agent3O4Raw cook replaces LiCoO2It is raw Piece, 2) before 900 DEG C carry out firing in 20 hours, there is no placing Li2CO3The state of raw cook is by Co3O4Raw cook in 1300 DEG C into It is burnt within row 5 hours, 3) there is no placing top load bearing board (Porous magnesia load bearing board), in addition to this, made in the same manner as example 2 Make positive plate and battery, carries out various evaluations.
Manufacturing condition and evaluation result
The manufacturing condition of example 1~17 is provided in table 1, and the evaluation result of example 1~17 is provided in table 2.In addition, as described above, Raw material A~H meaning shown in table 1 is as follows.It should be noted that the partial size of raw material powder as shown below is dissipated by laser diffraction Penetrate formula particle size distribution analyzer (MicrotracBEL Co. Ltd. system, Microtrac MT3000II) measurement.
Raw material A: the LiCoO of 5 μm of volume reference D50 partial size2Raw material powder
Raw material B: volume reference D50 0.2 μm of partial size of LiCoO2Raw material powder
Raw material C: the LiCoO of 15 μm of the volume reference D50 partial size through 700 DEG C be fired into of firing temperature2Raw material powder
Raw material D: volume reference D50 3 μm of partial size of LiCoO2Raw material powder
Raw material E: the raw material powder got similarly other than firing temperature is 900 DEG C with raw material C
Raw material F: the raw material powder that raw material C is crushed with ball mill
Raw material G: make the Co (OH) spherical using Co deposited synthesis2It is former that obtained synthesis is reacted in 800 DEG C with LiOH Feed powder end
Raw material H: the mixed raw material powder that raw material A, D and E are equably mixed to get
Table 1
Table 2

Claims (4)

1. a kind of sintered lithium complex oxide plate is the sintered lithium complex oxide plate of the anode for lithium secondary battery, Wherein,
The sintered lithium complex oxide plate has: multiple primary particles with layered rock salt structure combine obtained knot Structure, also,
The porosity is 3~30%,
Average air aperture be 15 μm hereinafter,
Open pore ratio is 70% or more,
With a thickness of 40~200 μm,
The average grain diameter of the multiple primary particle, i.e. primary particle size be 20 μm hereinafter,
The peak number of gas pore-size distribution is 1,
Volume reference D10, D50 and D90 stomata diameter meet D50/D10 >=2.5, D90/D50 >=2.5 and D90/D10 >=8.0 Relationship.
2. sintered lithium complex oxide plate according to claim 1, wherein
In the X-ray diffraction of the sintered lithium complex oxide plate, (003) crystal face diffracted intensity is relative to (104) crystalline substance Ratio [003]/[104] of the diffracted intensity in face are 5.0 or less.
3. sintered lithium complex oxide plate according to claim 1 or 2, wherein
The sintered lithium complex oxide plate with a thickness of 80~200 μm.
4. sintered lithium complex oxide plate according to claim 1 or 2, wherein
The sintered lithium complex oxide plate with a thickness of 100~200 μm.
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